Polymers formed from the reaction of a mixture of a polyepoxide and a polyester and an unsymmetrical disubstituted hydrazine

ABSTRACT

Polymers comprising the reaction product of: A. unsymmetrical disubstituted hydrazine and B. a material selected from the group consisting of: 1. EPOXY-ESTERS HAVING AT LEAST ONE REACTIVE EPOXIDE GROUP AND AT LEAST ONE REACTIVE CARBOXYLIC ACID ESTER GROUP, AND 2. MIXTURES OF POLYEPOXIDES HAVING A PLURALITY OF REACTIVE EPOXIDE GROUPS AND POLYESTERS HAVING A PLURALITY OF REACTIVE ESTER GROUPS. These polymers find utility as decorative and/or protective coatings when applied to substrates.

v United States Patent Sedor et al.

[4 1 June 20, 1972 [54] POLYMERS FORMED FROM THE REACTION OF A MIXTURE OF A POLYEPOXIDE AND A POLYESTER AND AN UNSYMMETRICAL DISUBSTITUTED HYDRAZINE Edward A. Sedor, Bloomington; Robert C. Slagel, Savage, both of Minn.

Assignee: Ashland Oil, Inc., Ashland, Ky.

Filed: Nov. 12, 1970 Appl. N0.: 89,147

Related US. Application Data Division of Ser. No. 714,322, March 19, 1968, Pat. No. 3,565,868.

lnventors:

US. Cl. ..260/18 PF, 260/2 EP, 260/ l 8 EP, 260/47 EP, 260/835 Int. Cl ..C08g 45/00 Field of Search ..260/18 PF, 47 EP, 47 EN, 2 EP, 260/2 N, 835. 2 EC [56] References Cited UNlTED STATES PATENTS 2,371,133 3/1945 Graenacher et al. ..260/404.5

Primary E.\'aminer-Donald E. Czaja Assistant Examiner-Eugene C. Rzucidlo v AnorneySherman J. Kemmer et al.

[57] ABSTRACT These polymers find utility as decorative and/or protective coatings when applied to substrates.

1! Claims; No Drawings POLYMERS FORMED FROM THE REACTION OF A MIXTURE OF A POLYEPOXIDE AND A POLYESTER AND AN'UNSYMMETRICAL DISUBSTITUTED HYDRAZINE This is a division of application Ser. No. 714,322, filed Mar. 19, 1968, now US. Pat. No. 3,565,868.

The present invention relates to polymers comprising the reaction product of:

A. unsymmetrical disubstituted hydrazine and B. a material selected from the group consisting of:

l. epoxy-esters having at least one reactive epoxide group and at least one reactive carboxylic acid ester group, and

2. mixtures of polyepoxides having a plurality of reactive epoxide groups and polyesters having a plurality of reactive ester groups,

wherein the reactants are substantially free of acid groups.

Suitable unsymmetrical disubstituted hydrazines are those of Formula 1:

N-NH:

wherein R and R can be alkyl, cycloalkyl, or aralkyl radicals of one to 30 carbon atoms. Examples of suitable alkyl radicals include, among others, heptacosyl, cyclohexyl, t-butyl, isopropyl, ethyl, and methyl. Lower alkyl radicals are preferred. Examples of suitable aralkyl radicals include, among others, benzyl, 2-phenyl-propyl, and 3-naphthyl-butyl. When R and R together represent a single divalent organic radical, this radical can be a ring of three to l0, preferably four to six, carbon atoms with the optional inclusion of one or two hereto atoms such as oxygen, sulfur, and nitrogen. Examples of suitable unsymmetrical disubstituted hydrazines include, among others, l-allyl-l-benzylhydrazine, l-cyclohexyll-ethylhydrazine, l-aminopyrrolidine, 4-aminomorpholine, amino hexamethylene imine, l-aminopiperidine, 1-amino-4- phenylpiperazine, l-amino-4-benxoylpiperazine, l-aminoperhydroindole, l-methyl-l-pentacosyl hydrazine, l-ethyl-lmethyl hydrazine, and l-l-dimethyl hydrazine which is most preferred because of its reactivity, cost and availability. Compounds such as l,4-diamino piperazine having in effect two unsymmetrical hydrazine groups are also within the broad scope of the present invention.

The epoxy-esters useful in the present invention are those having at least one reactive epoxide group by which is meant a moiety of Formula ll:

and at least one carboxylic acid ester group by which is meant a moiety offormula II]:

(III) The epoxide moiety of Formula I] can be internal, wherein each carbon atom of the oxirane ring is attached to at least one organic radical or, more preferably, is terminal, wherein at least one carbon atom of the oxirane ring is attached to two hydrogen atoms. Suitable carboxylic acid ester groups are those which are generally saponifiable ester groups. Whether these groups are saponifiable can be determined by mixing the carboxylic acid ester with sodium hydroxide according to well-known procedures. A broad class of suitable epoxy-esters are those of Formula lV:

wherein R is alkyl, and is preferably lower alkyl; R. is hydrogen or a monovalent organic radical such as alkyl, aryl, aralkyl and alkaryl; R is a divalent organic radical such as alkylene and preferably lower alkylene, cycloalkylene, phenylene, lower alkyl phenylene, and phenyl lower alkylene.

Other classes of suitable epoxy-esters include those of Formulas V through Vlll, below. wherein n is an integer from I to 30, preferably 1 to 8 inclusive:

C r-CH-{CHz)COCnH n+ wherein m is an integer from 1 to 9 inclusive;

wherein x and y are integers from 0 to 15 with the proviso that x-l-y is equal to or less than 15;

(VII) h C 0 c n ZnH and (VIII) 0 as well as epoxidized triglyceride oils such as epoxidized linseed oil or epoxidized soybean oil, sold as ADMEX H0 and ADMEX 7l 1. The polyepoxides useful in the present invention are those having a plurality of reactive epoxide groups. A broad class of suitable polyepoxides are those of Formula 1X:

wherein R and R are independently selected from the group consisting of hydrogen and monovalent organic radicals such as alkyl, cycloalkyl, aryl, aralkyl and alkaryl; R is an organic radical such as alkylene, arylene, or cycloalkylene; n is an integer from I to 4 inclusive but is preferably l: and q is O to l, with the proviso that when q is 0, n is l Other suitable polyepoxides include those of Formulas X through XVI, below:

wherein n is an integer from 0 to 12 inclusive;

(XII) R wherein R is H or CH (XIII) 0\ cm-cn-cm-o{cnr}-o-om-cfi-om wherein n is an integer from I to 4 inclusive; 5

(XIV) CHz-O-CHr-Cfi-CH:

CH: O R

! l0 CH20-'CH2 CH -'CH2 wherein R is H or O-OH C CHz l5 l l Ga en?- L J.

wherein n is 2 or 3;

(X I) CH;

and the polymers thereof sold under the tradename EPON." In general, these polymers are. the reaction product of bisphenol-A and an epihalohydrin, preferably epichlorohydrin;and compoundssuchas: wv wherein R is H or lower alkyl,- and other similar compounds disclosed in British Pat. No. 1,060,848. I

The polyesters useful in the present invention are compounds having aplurality of carboxylic acid ester moieties of Formula III. A broad class of suitable polyesters are those of Formula XVIII;

(XVIII) wherein R and R are alkyl, preferably lower alkyl and most preferably methyl; R is an organic radical and preferably an aliphatic or aromatic radical such as alkylene, preferably lower alkylene, lower cycloalkylene, phenylene, biphenyl, or napthylene; the preferred alkylene radical being (CH m being an integer from I to 'l l inclusive; wherein r is 0 or I and n is an integer from I to 4 inclusive and is preferably 1.

Examples of suitable polyesters include, among others, dimethyl fumarate, diethyl maleate, diisopropyl terephthalate, di-t-butyphthalate, dodecyl-methyl phthalate, methyl-ethyl itaconate, dimethyl. oxalate, methyl-ethyl-malonate, 1,2,4- benzenetricarboxylic acid trimethyl ester, 2,6-naphthalene dicarboxylic acid dimethyl ester, as well as those of Formulas XIX through XXIII:

O O a g 1 H300 -OCH:

Except where otherwise indicated, the radicals R through R are preferably hydrocarbon radicals but can be substituted with one or more, preferably one to three, substituents which are substantially inert to the reactants employed in the process of the present invention. Examples of suitable substituents include, hydroxyl, mercapto, and lower alkoxy such as methoxy. The reactants and therefore the radicals R through R should be substantially free of acid groups, such as carboxylic acid groups, which yield hydrogen ions in polar media.

The polymers of the present invention are produced by mixing stoichiometric amounts of the reactants at temperatures of 0 to 150 C, preferably 20 to C, for periods of 5 minutes to 7 days, preferably l hour to 3 days within the preferred temperature range; at atmospheric pressure generally or at subatmospheric pressures or superatmospheric pressures when volatile reactants are employed. The reaction can be conducted without a solvent or in the presence of solvents in amounts up to infinite dilution. Suitable solvents include water and lower alkanols such as t-butanol or isopropanol, although the latter are preferred. When the reactants comprise an unsymmetrical disubstituted hydrazine and an epoxy ester, the reaction proceeds according to Equation 1:

wherein R, R R, R", R, and p have the above-defined meanings. when the reactants comprise an unsymmetrical disubstituted hydrazine, a polyepoxide and a polyester, the reac- EXAMPLE 3 tion proceeds according to Equation 2:

The procedure of Example 2 is repeated except that 19.4 g,

of dimethyl terephthalate is used in place of the dimethyl l (Eq. 2) 2H2N-N R3O(IL/R5\(I;OR4 IUCfl CH R- -Cfi- CHR 1?; 1 I J L IN- -N NCHCH R -CHOHl 1 N- R OH won.

R2 R OH H R5 B.2

wherein R, R, R, R, R, R, R, R", q and r have the aboveadipate. A solid precipitates near the end of the reaction. All defined meanings. l5 solvent is evaporated in vacuo and the solid dissolved in The polymers of the present invention can be pyrolyzed by chloroform A film is spread on a glass plate, air dried, and heating to temperatures of 150 to 200 C. The pyrolysis is bethen baked at 160 C for 45 minutes to give a clear yellow, lieved to first split the polymer to form a diisocyanate and a brittle coating. The lR results are similar to those of Example bis(B-hydroxy tertiary amine) which then re-reacts to give a 2.

polyurethane with pendant tertiary amine groups. The tertiary amine can also act as a catalyst for the formation of the polyu- EXAMPLE 4 h Since the pyl' y P y of the Present ihveh' This example illustrates the synthesis of a polymer of the are waiehsoluble Whereas the Pyrolyzed P y are present invention which is the reaction product of an unsym- WaleFfeSiSlant, these P y can be applied as aqueous metrical disubstituted hydrazine and an epoxy ester. dispersions to a wide variety of substrates by procedures such In a 250 1 round bottom fl k fin d i h a nden as brushing p y pp followed y Pyrolysis to stirrer and reagent dropping funnel are placed methyl-10,! l-

durable, water-resistant, protective and/or decorative epoxymndecanenoate (10 8' Q0447 mole) and isopropanol i liz i rivention is further illustrated b the followin xam (50 ml). To the flask is added Slowly a Solution of 1 1 dimemfl ples in which all parts and percentages are by weigh? :nless hydrazine (3 0-0447 mo-le) lsopmpanol (50 ml) over a penod of 1 hours. The stirrer IS turned on and the flask and otherwise indicated. These non-limiting examples are illustrative of certain embodiments designed to teach those skilled in the art how to practice the invention and to represent the best its contents permitted to agitate for 2 days whereupon a small amount of the reaction mixture is removed form the flask, spread as a film on a salt plate, dried at 102 C for l hour and mode contem lated for can in out the invention.

P y g then baked at l70 C for 9 hours. The film lS hard, scratch re- EXAMPLE 1 sistant, and dark brown in color. The IR spectrum shows loss of the aminimide band at about 1,580 cm and appearance of In pressure home are placed d'methyl a band near 1,700 cm attributed to absorption of urethane l,l-dimethyl hydrazine, and 7.l g, freshly distilled l,7-octadicne dicpoxide in 50 ml. of isopropanol. The mixture is 40 stirred at room temperature for 72 hours. Infrared (IR) analy- EXAMPLE 5 sis shows the presence of ester so the reaction is continued for 3 more days. At this point the reaction mixture has turned cloudy. A polymer precipitates out in acetone to give a white hygroscopic solid which is soluble in methanol and water but lepoxyuhdecahehohme is replaced by an equimoiar insoluble in acetone, chloroform, benzene and hexane. The inamount of glycidyl (P'cafbomethoxy p y l the reac frared spectrum shows bands at 3,280 (OH stretch) and 1,590 n mixture is agitated overnight C and the mm was (aminimide) cm". baked at 165 C for 30 minutes. The IR spectrum shows logs The polymer is dissolved in water, spread onto a glass plate 0f the aminimide band at about l ,580 cm and appearance of and dried in an oven at l00 C for 3 hours. The resultant coata band near l,700 cm attributed to absorption of urethane ing is sticky to the touch. The plate is replaced in the oven and groups. the temperature raised to l60 C and held for 14 hours. A hard (Sward No. of 44), water-insoluble film results which ad- EXAMPLE 6 heres strongly to thE The procedure of Example 4 is repeated employing the EXAMPLE 2 same times, reactants and conditions except that the methyll0,l l-epoxy undecanenonate is replaced succesively by epoxy lnto a l-liter flask are placed 17.4 g, dimethyl adipate and esters of Formulas XXIV and XXV with similar results. 12.0 g, l,l-dimethyl hydrazine in [50 ml of isopropanol. To the stirred solution is added 36.0 g, Epon 828 (Shell Chemical Co.). The resulting mixture is stirred at room temperature for H l week. A sample of the product is evaporated in vacuo. The (XXIV) 0 groups.

The procedure of Example 4 is repeated employing the same times, reactants, and conditions except that the methylinfrared spectrum shows aminimide absorption at 1,575 cm as well as some ester absorption at 1,735 cm.

The reaction mixture is evaporated until a solution having a H u Sl percent non volatile content is obtained. The solution 18 (XXV) C L then spread on a glass plate and air dried. The resultant film is 7, then baked as follows:

a. l00 C for 45 minutes to give a clear, colorless, fairly hard film. IR still shows aminimide and OH absorption. b. [60 C for 45 minutes to give a clear yellow filmSward Although the invention has been described in considerable hardness of 26. IR no longer shows aminimide absorption detail with reference to certain preferred embodiments but does show new absorption at 1,700 cm. thereof, it will be understood that variations and modifications Epon 828 is described as the condensation product of l can be effected within the spirit and scope of the invention as mole of bisphenol-A with 2 moles of epichlorohydrin. described above and as defined in the appended claims.

What is claimed is: 1 wherein n is an integer from to l2 inclusive. 1. A polymer prepared by reacting a po yepox de, a 3, The polymer of claim I wherein said polyepoxide is an polyester and an unsymmetrical disubstituted hydrazine of the epoxidized triglyceride oil. formula: 4. The polymer of claim 3 wherein the epoxidized R triglyceride oil is epoxidized soybean oil. 5. The polymer of claim I wherein said polyepoxide is a resinous reaction product of bisphenol-A and epihalohydrin,

2 6. The polymer of claim 1 wherein R and R are lower alkyl in which R and R when taken singly, represents the same d n i l,

or different alkyl, cycloalkyl, aralkyl radical, or when 7. The polymer of claim 1 wherein R and R are methyl. taken together with the nitrogen atom to which they are 8. The polymer of claim I wherein R is lower alkylene, attached, represent a cycloaliphatic radical having from lower cycloalkylene, phenylene, or naphtylene. three to 10 atoms; 9. The polymer of claim 1 wherein R is -C H2 wherein said polyepoxide has the formula: wherein m is an integer from l to l l inclusive. j

0 0 10. A polymer of claim 1 having repeating units of the forl m cfi cn w cfi cn m a i- R h-N N- 3H-cH R CH-CH I I -N L 1 A I I R2 R6 OH OH R9 R2 in which R and R" represent hydrogen, alkyl, cycloalkyl, wherein:

aryl, aralkyl or alkaryl, R" represents alk lene, a lene or R and R represent the same or different alkyl, cycloalkyl cycloalkylene, andq is 0 or I; or aralkyl radicals or together represent a cycloaliphatic and wherein said polyester has the fonnula: radical, having from three to 10 atoms,

0 O R represents an alkylene, lower cycloalkylene, phenylene, a ll Fll biphenyl or naphthylene radical, R O C' R I 0T0 n R and R are independently selected from the group consisting of hydrogen alkyl, cycloalkyl aryl, aralkyl and alin which R and R" are alkyl, R is alkylene, lower cycloalkaryl,

kylene, phenylene, biphenyl or naphthylene, r is 0 or 1, an alky y n cycloalkylene radical, and n is an integer from 1 to 4 inclusive, with the proviso qf 0 l, and thatwhenris0,n isl. rlsool'l- 2. The polymer of claim 1 wherein said polyepoxide is of the The P y of claim 10 when?!" and R2 are lower lformula: kyl, R and R are lower alkylene, R and R" are independently 0 selected from the group consisting of hydrogen and lower all k l. a r cu tura -on on, y

\ 40 at I* 

1. EPOXY-ESTERS HAVING AT LEAST ONE REACTIVE EPOXIDE GROUP AND AT LEAST ONE REACTIVE CARBOXYLIC ACID ESTER GROUP, AND
 2. MIXTURES OF POLYEPOXIDES HAVING A PLURALITY OF REACTIVE EPOXIDE GROUPS AND POLYESTERS HAVING A PLURALITY OF REACTIVE ESTER GROUPS. THESE POLYMERS FIND UTILITY AS DECORATIVE AND/OR PROTECTIVE COATINGS WHEN APPLIED TO SUBSTRATES.
 2. The polymer of claim 1 wherein said polyepoxide is of the formula: wherein n is an integer from 0 to 12 inclusive.
 3. The polymer of claim 1 wherein said polyepoxide is an epoxidized triglyceride oil.
 4. The polymer of claim 3 wherein the epoxidized triglyceride oil is epoxidized soybean oil.
 5. The polymer of claim 1 wherein said polyepoxide is a resinous reaction product of bisphenol-A and epihalohydrin.
 6. The polymer of claim 1 wherein R3 and R4 are lower alkyl and n is
 1. 7. The polymer of claim 1 wherein R3 and R4 are methyl.
 8. The polymer of claim 1 wherein R5 is lower alkylene, lower cycloalkylene, phenylene, or naphtylene.
 9. The polymer of claim 1 wherein R5 is - CH2 -m wherein m is an integer from 1 to 11 inclusive.
 10. A polymer of claim 1 having repeating units of the formula wherein: R1 and R2 represent the same or different alkyl, cycloalkyl or aralkyl radicals or together represent a cycloaliphatic radical, having from three to 10 atoms, R5 represents an alkylene, lower cycloalkylene, phenylene, biphenyl or naphthylene radical, R6 and R8 are independently selected from the group consisting of hydrogen alkyl, cycloalkyl aryl, aralkyl and alkaryl, R7 is an alkylene, arylene or cycloalkylene radical, q is 0 or 1, and r is 0 or
 1. 11. The polymer of claim 10 wherein R1 and R2 are lower alkyl, R5 and R7 are lower alkylene, R6 and R8 are independently selected from the group consisting of hydrogen and lower alkyl. 